Nitraza amines and process for their production



United States Patent 3,234,282 NITRAZA AMINES AND PROCESS FOR THEIR PRODUCTION Milton B. Frankel, Menlo Park, and Charles H. Tiemau,

Modesto, Califi, assignors to Aerojet-General Corporation, Azusa, Caiiitl, a corporation of Uhio No Drawing. Filed Apr. 27, 1961, Ser. No. 105,877 11 Claims. (Cl. 260-583) This invention relates to new compositions of matter and a method for their preparation. In particular, this invention relates to nitraza amines having the general formula:

N0 R-Ii-A-NHZ wherein R can be any of the aminoalkyl, nitrazaalkyl, aminonitrazaalkyl, haloaminonitrazaalkyl, halonitrazaalkyl or aminohaloalkyl radicals; and A can be an alkylene or haloalkylene radical.

The nitraza amines of the present invention readily condense with B-geminal polynitro alcohols, such as 2,2,2- trinit-roethanol, to form high energy compounds, this type of reaction is more fully disclosed in assignees US. Patent No. 2,978,505, issued April 4, 1961. The perchlorate and nitrate salts of the nitraza amines of this invention are very high energy materials of the type disclosed in assignees US. Patent No. 2,978,511, issued April 4, 1961.

The high energy materials prepared from the nitraza amines of this invention by the method described above are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a -missile is disclosed in US. Patent No. 2,470,162, issued May '17, 1949. One way of using the high explosives in a device such as that disclosed in United States Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first vpelletized and then packed. A charge thus prepared is sutficien-tly insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.

Nit-raza amines were known prior to th present invention (assignees US. application Serial No. 666,273, filed June 13, 1957, now Patent No. 3,000,954). The known nitraza amines contained only a limited number of nitraza groups and possessed an insufiicient amount of oxygen for certain applications where a high oxygen balance is required. The method of preparing the known nitraza amines involved a complicated procedure going through an isocyanate using very eXPlOSiVe and toxic azides reacted with an acyl halide.

An object of this invention is to overcome the above mentioned disadvantages. Other objects and advantages will appear hereafter.

The novel process of this invention produces nitraza amines having the general formula:

which are prepared by nitrolyzing an alkanoyl amino compound having the general formula:

where R can be any of alkyl, .am-inoalkyl, nitrazaalkyl, nitro-alkyl, haloalkyl, aminonitrazaalkyl, nitronitrazaalkyl, halonitrazaalkyl, aminoni-troalkyl, halouitnoalky-l, aminohaloalkyl, aminonitrazanitroalkyl, nitrazani-troh-aloalkyl or aminonitrazahaloalkyl radical-s; A is either an alkylene or haloalkylene radical; R" can be any of the following radicals, alkyl, alhanoylaminoalkyl, nitroalkyl, haloalkyl, nitroalkanoylaminoalkyl, haloalkanoylaminoalkyl, halonitroalkyl or nitrohaloallcanoylaminoalkyl; and Y is an alkanoyl radical such as the following: acetyl, formyl, propanoyl, butyryl, benz-oyl, methanesulfonyl or benzencsulf-onyl. Nitrolysis is selective to the secondary aminoacyl radicals so that n-itrazaacylamino compolulds are produced. Hydrolysis with a mineral acid or base removes acyl radicals from the primary amino groups and forms a nitraza amine salt of the mineral acid. The nitraza amine salt is neutralized with a basic material to produce the free nitraza amine. In the instance where a basic hydrolysis is used, the free amine is produced directly. Mixtures of the above alkanoyl compounds can be used.

The corresponding free nitraza amines are generated from their mineral acid salts by neutralizing the salts with inorganic basic salts of alkali or alkaline earth metals, such as hydroxides or carbonates, or weak organic acid salts, such as acetates, of alkali or alkaline earth metals. For reasons of convenience and economy, I prefer to use sodium hydroxide as the amine generating agent, but other suitable generating agents, such as calcium hydroxide, magnesium hydroxide, sodium carbonate, lithium acetate, strontium formate, etc, can be employed for this purpose.

To more clearly illustrate this invention, the following examples are presented. It is to be understood, however, that these examples are presented merely as a means of illustration, and are not intended to limit the scope of the invention in any way.

EXAMPLE I Preparation 0 f N ,N ,N 'N 'N -pentaacetyl diethylenetriamine To 4080 g. (40.0 moles) of acetic anhyd-ride was added, dropwise, 515 g. (5.0 moles) of redistilled diethylenetriamine, keeping the temperature of l0l5 C. by external cooling. The solution was warmed to room temperature and then refluxed under a 20 plate Oldersh-aw column for 30 hrs., during which time the theoretical amount of acetic acid was collected. The residue was concentrated in vacuo, leaving a viscous dark brown oil which solidilied. The product was recrystallized from 3 1. of 2- propanol to give 823 g. (52.7%) of light yellow crystals, M.P. 106-108" C. A second recrystallization gave as a white solid N,N,N'N,N"-pen-taacetylidiethylenetriamine; M. P. 109110 C.

EXAMPLE II Nitrolysis of N,N,N,N',N"-pentaacetyldiethylenetriamine with nitric acid and trifluoroacetic anhydride To ml. (0.58 mole) of trifiuor-oacetic anhydride was added dropwise 16.8 ml. (0.4 mole) of 9899% technical nitric acid, keeping the temperature at 0 C. to 20 C. Then 31.3 g. (0.1 mole) of N,N,NN',N"-pentaacetyld'iethylenetriamine was added. The solid dissolved and the solution was allowed to stand and react in an ice-bath (0 C.) for 65 hrs. The reaction mixture was concentrated in vacuo. The residue was dissolved in methylene chloride, washed with saturated sodium carbonate solution, dried, and concentrated, leaving 28.8 g. (91.0%) of N,N,N',N tetraacetyl-N"-nitrodiethylenetriamine as a white solid, M.P. -122" C. Recrystallization from ethanol raised the melting point to 122-123 C.

3 EXAMPLE 1n Nitrolysis with nitrogen pentoxide in trifluoroacet'ic acid A mixture of 6.26 g. (0.02 mole) of N,N,N,N"-pentaacetyldiethylenetriamine, 12.0 g. (0.11 mole) of nitrogen pentoxide, and 10 ml. (0.16 mole) of trifluoroacetic acid was allowed to stand and react in an ice-bath C.) for 43 hrs.-, and then concentrated in vacuo. Working up in the same manner as described in Example 11 above, there was obtained 5.1 g. (80.8%) yield of N,N,N',N'-tetraacetiyl-N"-nitrodiethylenetriamine, M.P. 12l122 C.

EXAMPLE IV Nitrolysis with nitrogen pentoxide in dichloroacetic acid A mixture of 6.26 g. (0.02 mole) of N,N,N',N',N"- pentaacetyldiethylenetriamine, 10.8 g. (0.1 mole) of nitrogen pentoxide, and 38.7 g. (0.3 mole) of dichloroacetic acid was allowed to stand and react in an ice-bath (0 C.) for 24 hrs. The reaction mixture was poured on ice and a saturated sodium carbonate solution was added until the resulting pH of the solution was 10. The product was collected and recrystallized from ethanol to give 4.52 g. (71.4%) of N,N,N',N-tetraacetyl-N"-nitrodiethylenetriamine as white crystals.

EXAMPLE V Preparation of 3-nitraza-1,S-pentanediamine dihydrochloride A mixture of 31.6 g. (0.1 mole) of N,N,N',N'-tetraacetyl-N-nitrodiethylenetriamine and 50 ml. of 37% hydrochloric acid was refluxed for 4 hrs. The reaction mixture was cooled and diluted with 50 ml. of methanol. The product was collected and dried to give 19.7 g. (89.1%) of white crystals, M.P. 259263 C. Recrystallization from 78% ethanol raised the melting point to 261-263" C.

- EXAMPLE VI Preparation of 3-nitraza-1,5-pentanediamine In a 3-liter S-necked flask, fitted with a mechanical stirrer, thermometer, and dropping tunnel was placed a suspension of 290 g. (1.31 moles) of 3-nitraza-1,5-pentanediamine dihydrochloride and one liter of methanol. The mixture was cooled to 05 C. and a solution of 104.9 g. (2.62 moles) of sodium hydroxide in one liter of methanol was added dropwise. After the addition was complete, the mixture was stirred for an additional 30 minutes at 05 C. The precipitate of sodium chloride was removed by filtration and washed with methanol. The methanol solution contained 3-nitraza-1,5-pentanediamine.

EXAMPLE VII Preparation of 3,6-dinitraza-1,8-octanediamine A 1.4069 N solution of sodium methoxide in methanol (142.2 ml., 0.2 mole) was added dropwise with stirring at 0 to 5 C. to a suspension of 30.9 g. (0.1 mole) of 3,6-dinitraza-l,8-octane diamine dihydrochloride in 75 ml. of methanol. The mixture was stirred for 30 minutes at 0 to 5 C., and the precipitate of sodium chloride was removed by filtration and washed with methanol. The solution contained 3,6-dinitraza-l,8-octane diamine.

EXAMPLE VIII N itrolysis The procedure of Example II, above, was repeated except the solution was allowed to stand and react at 2l C. for 168 hours. A yield of 87.6% was obtained.

EXAMPLE 1X N itrolysis 5-brom0 N,N',N",N" -tetraacetyl-1,3,7-octyltriamine was subjected to selective nitrolysis according to the procedure described in Example IV, above, except that sulphur dioxide was substituted for the dichloroacetic acid used in the above example. The temperature was maintained at 20 C. The reaction time was 160 hours. 5-bromo-3,7 dinitraza N,N"-diacetyl-l-octylamine was obtained in a yield of 67.7%.

EXAMPLE X Nitrolysis N,N,N',N',N",N-hexaacetyltriethylenetetramine was subjected to nitrolysis according to the procedure described in Example 11, above. The solution was allowed to stand and react at 20 C. for seven days, the temperature was then raised to 0 C. where it was held for 3 days. N,N,N',N-tetraacetyl-N,N"'-dinitrotriethylenetriamine, M.P. 112-113 C., was obtained in a yield of 85.7%.

EXAMPLE XI Nitrolysis with nitric acid and trichloroacetic anhydride N,N,N,N',N"-pentaacetyldiethylenetriamine was subjected to nitrolysis according to the procedure described in Example 11, above, except that trichloroacetic anhydride was used rather than trifluoroacetic anhydride. N,N,N,N'-tetraacetyl-N"-nitrodiethylenetriamine was obtained in a yield of 11.6%.

EXAMPLE XII Nitrolysis with nitrogen pentoxide in dichloroacetic acid N,N,N,N,N"-pentaacetyldiethylenetriamine was subjected to nitrolysis according to the procedure described in Example 111, above, except that dichloroacetic acid was used rather than trifluoroacetic acid. N,N,r ,N tetracetyl-N"-nitrodiethylenetriamine was obtained in a yield of 68.2%.

EXAMPLE XIII Acetylation Triethylenetetramine was subjected to acetylation according to the procedure defined in Example 1, above. N,N,N,N",N"'-hexaacetyltriethylenetetramine, M.P. 150- 151 C., was obtained in a yield of 72.0%.

EXAMPLE XIV Hydrolysis N,N,N,N' tetraacetyl N,N" dinitrotriethylenetetramine was subjected to hydrolysis according to the procedure described in Example V, above. 3,6-dinitraza-1,8-octanediamine dihydrochloride, M.P. 285- 295 C., was obtained in a yield of The reaction temperatures are not critical in the practice of this invention, the effect of temperature variation being to vary the reaction rates of the alkanoylation, nitrolysis, hydrolysis and neutralization reactions. It has been found, however, that particularly favorable results are obtained in the nitrolysis reaction it the temperature is maintained between about 0 C. and about -20 C.

The nature of the alkanoyl group introduced by alkanoylation is not critical since it merely serves as a protective agent for the amino radical. Any of the following alkanoylatin-g materials can be used: acid halides, acids and anhydrides, including acetic anhydride, butyryl chloride, acetylchloride, propionic acid, butyric acid, formyl chloride, butyric anhydride, rnethanesulfonyl chloride, benzenesulfonyl chloride and benzoyl chloride. The preferred alkanoyl radicals do not contain aromatic rings since in subsequent nitrolysis these rings will tend to undergo side reactions.

It will be appreciated that a large number of alkanoylamino compounds, including the following, can be nitrolized according to this invention:

N,N,N'-tritormyl-1,3-butanediamine, N,N,N'-tributyryl-1 ,4-pentanediamine, N,N,N-trimethanesulfonyl-1,3-hexanediamine, N,N,N'-tripropanoyl-4,4-dinitro-1,3-butanediamine,

N,N,N-tribenzoyl-5,5,5-trinitro1,4-pentanediamine, N,N,N-tribenzenesulfonyl-5,S-dinitro-1,3-hexanediamine, N,N,N'-triacetyl-5,G-dichloro-1,4-octanediamine, N,N,N'-triformyl-6-bromo-l B-heptanediamine, N,N,N-tripropanoyl-4-chloro-1,3-butanediamine, N,N,N,N",N"-pentaformyl-l ,4,6-hexanetriamine, N,N,N,N',N'-pentaacetyl-l,3,9-nonanetriarnine, N,N,N',N,N"-pentabutyryl-1,3,5-pentanediamine, N,N,N,N",N"-pentapropanoyl-1,4,6-hexanetriarnine, N,N,N,N",N"-pentaacetyl-5,5-dinitro-l,3,6-hexanetriamine, N,N,N',N, "-pentaformy1-4,4-dinitro-1,2,5-pentanetriarnine, N,N,N,N",N"-pentapropanoyl-6,6,7-trinitro-1,4,8-

octanetriamine, N,N,N,l ",N"',N"-hexabutyryl-8,8-dinitro-1,3,6,9-

nonanetitrarnine, N,N,N,N",N"',N"", "-heptabenzoyl-7,7-dinitrol,3,5,8,lO-deconepentamine, N,N,N,N",N"',N-hexaformyl-5,S-dinitro-l,3,7,9- nonanetitramine, N,N,N'-triacety1-5-bromo-6,6,6-trinitro-l,3-hexyldiamine, N,N,N-tripropanoyl-4-chloro-5,5,S-trinitro-l,3-

pentyldiamine, N,N,N-triformyi-7,7-dichloro-6,6-dinitro-1,4- heptyldiamine, N,N,N',N"-tetraacety1-4-chlore-7,7,7-trinitro-l,3, 6-heptyltriamine, N,N,N,N"-tetrabutyryl-7-chloro-4,4-dinitro-l, 3,6-hetypltriamine, N,N,N',N"-tetrapr0p-anoyl-6,6-dichloro-8-nitro-1,4,7-

octyltriamine.

Nitrolysis is accomplished using either nitric acid or nitrogen pentoxide in a liquid such as the halogenated organic solvents, methylene chloride, ethylene dichloride, or carbon tetrachloride; the organic halo acids such as trifiuoroacetic acid, perfluoropropionic acid, perfluorobutyric acid, monofluoroacetic acid, dichloroacetic acid; the organic halo acid anhydrides such as trifluoroacetic anhydride, trichloroacetic anhydride, perfiuoropropionic anhydride, monofiuoroacetic anhydride; and the oxides of sulfur such as sulfur dioxide and sulfur trioxide. Our preferred agents include nitric acid in trifiuoroacetic anhydride and nitrogen pentoxide in trifiuoroacetic acid.

Hydrolysis is accomplished using either mineral acids or bases, for example, sulfuric acid, sulfonic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, calcium hydroxide and boriurn hydroxide. The reaction can be carried out using dilute or concentrate or bases at room or elevated temperatures. Generally, increasing the temperature and concentration increases the rate of reaction. Mixtures of hydrolyzing acids or mixtures of hydrolyzing bases can be used.

It will be appreciated that a Wide variety of nitrazeamine compounds are included in the teachings of this invention. For example,

3-nitraza- 1 ,4-butanediamine,

3 ,6-dinitrazaheptylamine, 2,4-dintraza-1,S-pentanediamine, 3,6-dinitraza-1,8-octanediamine, 6-nitraza-LS entanediamine, 3,6-dinitraza-1,8-octanediamine, 8bromo-3 ,fi-dinitraza-l-octylamine, 5-bron1o 3,7-dinitraza-1-octylamine, 2-bromo-3,5-dinitraza-l ,S-hexanediamine, 2,6-dichloro-4-nitraza-1,8-octanediamine, 2-chloro-4,6,8-trinitraza-1-nonylamine, 6-chloro-2,5-dinitraza-1,8-octanediamine, 6-methyl-2,4-dinitraza-l-heptylamine, 7,7-dichloro-4-nitraza-1,S-Octanediamine, 6,7-dichloro-3,S-dinitraza-l,S-octanediamine,

6 6,6,2-tribromo-4-nitraza-1,7-heptanediamine, 2,2-dichloro-4-nitraza-1,6-hexanedamine, 8,8-dibrorno-2,4,6-trinitraza-l-octylamine, 7,7-dichloro-6-nitraza-1,8-octanediamine, 6-chloro-6-methyl-2,4-dinitraza-1,7-heptanediarnine. 7 ,7 ,7-trinitro-2,5 -dinitraza-1-heptylamine,

7 ,7-dinitro-2,5-dinitraza-l-octylamine, 6-nitro-2,4-dinitraza-l-hexylamine and 7,7-dinitro-3,5-dinitraza-l-heptylarnine.

It will be appreciated that if mixtures of starting materials are used, mixtures of the above products will resuit.

The nirazaamines of this invention can be used as the starting material to prepare the corresponding nitraza isocyanates by reacting nitraza amines with phosgene.

It will be understood that various modifications may be made in this invention without departing from the spirit thereof or the scope of the claims.

We claim:

1. The nitraza amines having the formula:

wherein R is selected from the group consisting of lower aminoalkyl, lower nitrazaalkyl, lower aminonitrazaalkyl, lower nitronitrazaalkyl, lower chloroarninonitrazaalkyl, lower bromoaminonitrazaalkyl, lower chloronitrazaalkyl, lower bromonitrazaalkyl, lower aminochloroalkyl, and lower aminobromoalkyl radicals; and A is selected from the group consisting of lower alkylene, lower chloroalkylene and lower bromoalkylene radicals.

2. The nitraza amines having the formula:

Wehrein R is a lower nitraza alkyl radical, and A is a lower alkylene radical.

3. The nitraza having the formula:

wherein R is a lower amino alkyl radical, and A is a lower alkylene radical.

wherein R is a lower nitro nitraza alkyl radical, and A is a lower alkylene radical.

5. The nitraza amines having the formula:

wherein R is a lower amino nitraza alkyl radical, and A is a lower alkylene radical.

6. 3-nitraza-1,5-pentane diamine, having the structural formula:

7. 3,6-dinitraza-1,8-octane diamine, having the structural formula:

8. 7,7-dinitro-3,5dinitrazal-heptylamine, having the structural formula:

$0 N02 N02 (IJHCH2NCHzNCHzCHZNH: N02

9. 5-bromo-3,7-dinitraza-1-octylamine, having the structural formula:

N02 Br IIIO: CHaNCHzCHCHzNCHzCHgNH:

7 10. The process which comprises reacting an alkanoylamino compound having the formula:

t R"N-ANY1 with a nitrolyzing agent selected from the group consisting of nitric acid and nitrogen pentoxide in a liquid selected from the group consisting of organic halo acids, halogenated organic solvents, oxides of sulfur, and organic halo acids anhydrides, to form nitrazaalkanoylamino com-pound having the formula:

1T? 02 "N,ANY1 and hydrolyzing said nitrazaalkanoylam no compound with acid to produce a nitraza amine salt, and neutralizing said nitraza amine salt to produce the free nitraza amine compound having the formula:

W R'N- A NH; wherein in the foregoing formulae, R is selected from the group consisting of lower alkyl, lower aminoalkyl, lower nitrazaalky-l, lower nitroalkyl, lower chloroalkyl, lower bromoalkyl, lower aminonitrazaalkyl, lower nitronitrazaalkyl, lower chloronitrazaalkyl, lower bromonitrazaalkyl, lower aminonitroalkyl, lower chloronitroalkyl, lower bromonitroalkyl, lower aminochloroalkyl, lower aminobromoakyl, lower aminonitrazanitroalkyl, lower nitrazanitrochloroalkyl, lower m'trazanitrobromoalkyl, lower aminonitrazachloroalkyl, and lower aminonitrazabromoalkyl radicals; R" is selected from the group consisting of lower alkanolyaminoalkyl, lower nitroalkyl, lower chloroalkyl, lower bromoalkyl, lower nitr'oalkanoylaminoalkyl, lower chloroalkanolyaminoalkyl, lower bromoalkanolyaminoalkyl, lower chloronitroalkyl, lower brornonitroalkyl, and lower nitrochloroalkanoylaminoalkyl and lower nitrobromoalkanolyaminoalkyl radicals; A is selected from the group consisting of lower alkylene and, lower chloroalkylene, and lower bromoalkylene radicals; and Y is an alkanoyl radical.

11. The process which comprises reacting an alkanoylamino compound having the formula:

f "NANY2 with a nitrolyzing agent selected from the group consisting of nitric acid and nitrogen pentoxitle in a liquid selected 8 from the group consisting of organic halo acids, halogen,- ated organic solvents, oxides of sulfur, and organic halo acids anhydrides, to form nitrazaalkanoylamino compound having the formula:

and reacting said nitrazaalkanoylamino compound with a base to produce the free nitraza amine compound having the formula:

wherein in the foregoing formulae, R is selected from the group consisting of lower alkyl, lower aminoalkyl, lower nitrazaalkyl, lower nitroalkyl, lower chloroalkyl, lower bromoalkyl, lower aminonitrazaalkyl, lower nitronitrazaalkyl, lower chloronitrazaalkyl, lower bromonitrazaalkyl, lower aminonitroalkyl, lower chloronitroalkyl, lower bromonitroalkyl, lower aminochloroalkyl, lower aminobromoalkyl, lower aminonitrazanitroalkyl, lower nitrazanitrochloroalkyl, lower nitrazanitrobromoalkyl, lower amino.- nitrazachloroalkyl and lower aminonitrazabromoalkyl radicals; R is selected from the group consisting of lower alkanoylaminoalkyl, lower nitroalkyl, lower chloroalkyl', lower bromoalkyl, lower nitroalkanoyaminoalkyl, lower chloroalkanolyarninoalkyl, lower bromoalkanoylaminoalkyl, lower chloronitroalkyl, lower bromonitroalkyl, lower nitrochloroalkanoylaminoalkyl and lower nitrobromoakanoylaminoalkyl radicals; A is selected from the group consisting of lower alkylene, lower chloroalkylene, and lower bromoalklene radicals; and Y is an alkanoyl radical.

References Cited by the Examiner UNITED STATES PATENTS 2,731,460 1/1956 Schenck et a1. 260-583 2,978,511 4/1961 Frankel 260-583 3,000,955 9/1961 Frankel 260583 OTHER REFERENCES Dombrow: Polyurethanes, Reinhold Publishing Corp., New York (1957), p. 14.

CHARLES B. PARKER, Primary Examiner.

LEON ZlTVER, JOSEPH P. BRUST, Examiners. 

1. THE NITRAZA AMINES HAVING THE FORMULA: 